Catalytic cracking process of a lipid-containing feedstock

ABSTRACT

A process for catalytic cracking of a lipid-containing feedstock is provided. The lipid-containing feedstock contains lipids derived from a diatomic microalgae species. The lipid-containing feedstock is contacted with at least one cracking catalyst at a temperature of at least 450° C., to obtain a product stream; and separating at least one hydrocarbon fraction from the product stream.

FIELD OF THE INVENTION

The present invention relates to a process for catalytic cracking of alipid-containing feedstock.

BACKGROUND OF THE INVENTION

Various processes for catalytic cracking of heavy hydrocarbons are knownin the art. In these processes, heavy hydrocarbons, such as heavy oilsand vacuum residues, are brought in contact with a cracking catalyst andare converted into lighter products having lower boiling points.Exemplary descriptions of such processes have been provided for instancein U.S. Pat. No. 4,917,790 and in U.S. Pat. No. 6,905,591.

However, with the diminishing supply of crude oil, use of renewableenergy sources is becoming increasingly important for the production ofchemicals and fuels. Plant and animal biomass, are being used to produceliquid and gaseous fuels through the catalytic cracking process. One ofthe advantages of using biomass is that the CO₂ balance is morefavourable as compared with the conventional hydrocarbon feedstock.

US2009/0047721 describes a process for producing hydrocarbons for use indiesel and jet fuels by subjecting lipids derived from algae to acatalytic cracking process. However, the products obtained through thiscracking process predominantly include a mixture of C2 to C5 olefins andneed additional chemical treatment to produce usable fuel products.

EP1970425 describes a process for producing gaseous and liquid fuels bycracking lipids derived from high viscosity carbon-based energy carriermaterials and WO-A-2009/000838, describes a process for producing biooils by cracking of lipids derived from aquatic biomass. However, thesereferences disclose using a cracking temperature of below 450° C., andonly yield products in low yields and with limited selectivity.

Kitazato et al. describe in their article titled “Catalytic cracking ofhydrocarbons from microalgae”, International Chemical Engineering,Volume 31, no 3, July 1991, a process for the production of gasoline bycatalytic cracking of hydrocarbons obtained from the microalgaeBotryococcus braunii Berkeley (a green algae). For the catalyticcracking process a commercial FCC zeolite was used. Exemplified reactionconditions included temperatures in the range from 450 to 500° C. AlsoKitazato et al. teach, however, that low temperatures of cracking (below450° C.) are necessary to ensure a high yield of gasoline. In addition,the use of a catalyst comprising 100 wt % zeolite is too expensive forcommercial operation.

It would be an advancement in the art if a process would be provided forcatalytic cracking of biomass with improved efficacy.

SUMMARY OF THE INVENTION

Accordingly, the present invention provides a process for catalyticcracking of a lipid-containing feedstock, the process comprisingcontacting the lipid-containing feedstock with at least one crackingcatalyst at a temperature of at least 450° C., to obtain a productstream; and separating at least one hydrocarbon fraction from theproduct stream; wherein the lipid-containing feedstock comprises lipidsderived from a diatomic microalgae species.

According to a further embodiment, the present invention provides agasoline product prepared from a hydrocarbon fraction of the at leastone hydrocarbon fraction.

According to yet another embodiment, the present invention provides aliquefied gaseous fuel composition comprising a liquefied gaseous fuelproduct prepared from a hydrocarbon fraction of the at least onehydrocarbon fraction, less than 1000 ppmw sulfur, and one or moreadditives.

DETAILED DESCRIPTION OF THE INVENTION

It was found that, when using lipids derived from a diatomic microalgaespecies as a feedstock, contrary to the teachings in the prior art, ahigher cracking temperature gives a higher conversion and hence morevaluable lighter products (that is, more products having a boiling pointbelow 221° C. such as, for example, LPG and gasoline).

The process according to the invention is further advantageous becausediatomic microalgae have high growth rates, utilise a large fraction ofsolar energy and can grow in conditions that are not favourable forterrestrial biomass. Additionally, diatomic microalgae consume CO₂ at ahigh rate, and may reduce the carbon footprint of the overall process.Further diatomic microalgae contain high concentrations of lipids.

It has now been found that cracking of a lipid-containing feedstock,that comprises lipids derived from a diatomic microalgae species, over acracking catalyst at a temperature of at least 450° C. results in adesirable product stream.

Diatomic microalgae as referred to in the present invention are a largeand diverse group of microorganisms living in an aquatic environmentthat have a cell wall comprising silica. They can be unicellular ormulticellular, but are preferably unicellular. The diatomic microalgaepreferably have a diameter smaller than 1 mm, more preferably a diametersmaller than 0.6 mm and still more preferably a diameter smaller than0.4 mm. The diameter is measured at its largest point. Most preferablythe diatomic microalgae comprise a diameter in the range from 0.5 to 200micrometer, even more preferably in the range from 1 to 100 micrometer.The diatomic microalgae can be cultivated under difficult agro-climaticconditions, including cultivation in freshwater, saline water, moistearth, dry sand and other open-culture conditions known in the art. Thediatomic microalgae can also be cultivated and genetically engineered incontrolled closed-culture systems, for example, in closed bioreactors.Preferably, the diatomic microalgae used in the present invention aremarine diatomic microalgae cultivated in fresh water, saline water orother moist conditions, more preferably marine diatomic microalgaecultivated in saline water. Yet more preferably, the marine diatomicmicroalgae are cultivated in open-culture conditions, for example, inopen ponds.

Lipids as referred to in the present invention are a group of naturallyoccurring compounds that are usually hydrophobic in nature and containlong-chain aliphatic hydrocarbons and their derivatives such as fattyacids, alcohols, amines, amino alcohols and aldehydes. Thelipid-containing feedstock as disclosed in the invention includes lipidsderived from marine diatomic microalgae. These lipids includemonoglycerides, diglycerides and triglycerides, which are esters ofglycerol and fatty acids, and phospholipids, which are esters ofglycerol and phosphate group-substituted fatty acids.

The fatty acid moiety in the lipids used in the invention ranges from 4carbon atoms to 30 carbon atoms, and includes saturated fatty acidscontaining one, two or three double bonds. Preferably, the fatty acidmoiety includes 8 carbon atoms to 26 carbon atoms, more preferably thefatty acid moiety includes 10 carbon atoms to 25 carbon atoms, againmore preferably the fatty acid moiety includes 12 carbon atoms to 23carbon atoms, and yet more preferably 14 carbon atoms to 20 carbonatoms. The lipids may contain variable amounts of free fatty acidsand/or esters, both of which may also be converted into hydrocarbonsduring the process of this invention. In one embodiment the lipids maybe composed of natural glycerides only. Alternatively, the lipids mayalso include carotenoids, hydrocarbons, phosphatides, simple fatty acidsand their esters, terpenes, sterols, fatty alcohols, tocopherols,polyisoprene, carbohydrates and proteins. It is to be understood thatfor the purpose of this invention, a mixture of lipids extracted fromdifferent diatomic microalgae sources can also be used in thelipid-containing feedstock.

The diatomic microalgae may be processed to extract lipids usingprocesses known in the art. The said processes may include the steps ofharvesting the diatomic microalgae, dewatering the diatomic microalgae,disrupting the diatomic microalgae's cell walls to liberate lipids, andthen extracting the lipids using solvents, supercritical fluids or otherextraction processes. In a preferred embodiment, the diatomic microalgaeare cultivated, harvested, dried, milled and then lipids are extractedusing a water immiscible solvent at 25° C. Suitable solvents for theextraction are organic solvents such as aromatic or aliphatichydrocarbons, higher alcohols, ethers and esters. Examples for suchsolvents are toluene, hexane, heptane, dimethyl ether, acetic acid esterand mixtures thereof. Other solvents include supercritical liquids, suchas supercritical carbon dioxide.

The extracted lipids may conveniently be isolated by evaporating thesolvent, or by other methods, such as membrane separation.

Preferably, the lipid-containing feedstock includes lipids in the rangeof 1 wt % to 50 wt %, more preferably in the range of 2 wt % to 40 wt %,more preferably in the range of 3 wt % to 30 wt %, and yet morepreferably in the range of 5 wt % to 20 wt %, based on the total weightof lipid-containing feedstock.

The lipid-containing feedstock further preferably comprises ahydrocarbon feedstock. That is, the lipids (also referred to as lipidfeedstock) may preferably be co-fed together with a hydrocarbonfeedstock. The co-feeding may be attained by blending the two feedstockstreams prior to entry into the cracking unit, or alternatively, byadding them at different stages.

The hydrocarbon feedstock preferably comprises hydrocarbons with aboiling point of at least 220° C., as measured by Gas ChromatographDistillation (GCD) according to ASTM D-6352-98. Preferably, the boilingpoints range from 220° C. to 650° C., more preferably from 300° C. to600° C. Furthermore, the hydrocarbon feedstock preferably has an initialboiling point above 180° C., as measured by Gas ChromatographDistillation (GCD) according to the methods described in ASTM D-6352-98.

In one embodiment the hydrocarbon feedstock includes hydrocarbons havinga mineral origin. Preferably such hydrocarbon feedstock comprises amineral oil or a derivative of a mineral oil. The hydrocarbon feedstockmay be a conventional fluid catalytic cracking feedstock. Examples ofthe hydrocarbon feedstock include high boiling, non-residual oils suchas straight run (atmospheric) gas oils, vacuum gas oils, flasheddistillate, coker gas oils, or atmospheric residue ('long residue') andvacuum residue (‘short residue’).

In another embodiment the hydrocarbon feedstock may include a paraffinicfeedstock, for example, an optionally hydroisomerised fraction of thesynthesis product of a Fischer-Tropsch reaction, or the fraction boilingabove the middle distillate boiling range of the effluent of fuelhydrocracker, also referred to as hydrowax. An advantage of using saidparaffinic feedstock in admixture with the lipids is that the aromaticcontent of gasoline fraction, can be reduced by co-processing theparaffinic feedstock. It has been found that on cracking a paraffinicfeedstock a gasoline having a very low aromatic content can be obtained.

Further, lipids derived from other biomass sources such as plant andvegetable oils may also be added to the lipid-containing feedstock as anadditional cracking feedstock.

Preferably, the total feed going into the catalytic cracking unit maycomprise the hydrocarbon feedstock in the range of 50 wt % to 99 wt %,preferably in the range from 60 wt % to 98 wt %, more preferably 70 wt %to 98 wt %, more preferably 70 wt % to 97 wt %, most preferably in therange of 80 wt % to 95 wt % based on the total weight oflipid-containing feedstock, the remainder being the lipid feedstock.

The process of catalytic cracking of the lipid-containing feedstockaccording to the invention preferably comprises a catalytic crackingstep, which may be followed with a regeneration step.

More preferably the catalytic cracking process includes a catalyticcracking step, in which the cracking reaction takes place in thepresence of a catalyst; a regeneration step, in which the catalyst isregenerated, for example by burning off the coke deposited on thecatalyst as a result of the reaction, to restore the catalytic activity;and a recycle step, wherein the regenerated catalyst is recycled to thecatalytic cracking step. The heat generated in the exothermicregeneration step is preferably employed to provide energy for theendothermic cracking step.

The catalytic cracking step comprises contacting the lipid-containingfeedstock with a cracking catalyst, preferably in the reaction zone of afluidized catalytic cracking (FCC) apparatus. The reaction temperaturepreferably ranges from equal to or more than 450° C. to equal to or lessthan 650° C., more preferably from equal to or more than 480° C. toequal to or less than 600° C., and most preferably from equal to or morethan 480° C. to equal to or less than 560° C. The pressure in thereaction zone preferably ranges from equal to or more than 0.5 bar toequal to or less than 10 bar (0.05 MPa-1 MPa), more preferably fromequal to or more than 1.0 bar to equal to or less than 6 bar (0.15 MPato 0.6 MPa). The residence time of the cracking catalyst in the reactionzone preferably ranges from equal to or more than 0.1 seconds to equalto or less than 15 seconds, more preferably from equal to or more than0.5 seconds to equal to or less than 10 seconds. The product streamobtained from the cracking step may be separated into one or morehydrocarbon fractions using, for example, a fractionator.

Preferably, a catalyst to lipid-containing feedstock mass ratio rangingfrom equal to or more than 3 to equal to or less than 8 is used.Preferably, the catalyst to feedstock mass ratio used is at least 3.5.The use of a higher catalyst to feedstock mass ratio results in anincrease in conversion.

The process according to the invention further preferably comprises acatalyst regeneration step. A regeneration step preferably may compriseburning off the coke to restore the catalyst activity by combusting thecracking catalyst in the presence of an oxygen-containing gas in aregenerator. The regeneration temperature preferably ranges from equalto or more than 575° C. to equal to or less than 950° C., morepreferably from equal to or more than 600° C. to equal to or less than850° C. The pressure in the regenerator preferably ranges from equal toor more than 0.5 bar to equal to or less than 10 bar (0.05 Mpa to 1MPa), more preferably from equal to or more than 1.0 bar to equal to orless than 6 bar (0.1 MPa to 0.6 MPa.

Cracking catalysts suitable for use in the process according to theinvention are well known in the art. Preferably, the cracking catalystcomprises a zeolitic component, and more preferably, an amorphousbinder. Examples of such binder materials include silica, alumina,titania, zirconia and magnesium oxide, or combinations of two or more ofthem.

The zeolite is preferably a large pore zeolite. The large pore zeoliteincludes a zeolite comprising a porous, crystalline aluminosilicatestructure having a porous internal cell structure on which the majoraxis of the pores is in the range of 0.62 nanometer to 0.8 nanometer.The axes of zeolites are depicted in the ‘Atlas of Zeolite StructureTypes’, of W. M. Meier, D. H. Olson, and Ch. Baerlocher, Fourth RevisedEdition 1996, Elsevier, ISBN 0-444-10015-6. Examples of such large porezeolites include FAU or faujasite, preferably synthetic faujasite, forexample, zeolite Y or X, ultra-stable zeolite Y (USY), Rare Earthzeolite Y (=REY) and Rare Earth USY (REUSY). According to the presentinvention USY is preferably used as the large pore zeolite.

The cracking catalyst can also comprise a medium pore zeolite. Themedium pore zeolite that can be used according to the present inventionis a zeolite comprising a porous, crystalline aluminosilicate structurehaving a porous internal cell structure on which the major axis of thepores is in the range of 0.45 nanometer to 0.62 nanometer. Examples ofsuch medium pore zeolites are of the MFI structural type, for example,ZSM-5; the MTW type, for example, ZSM-12; the TON structural type, forexample, theta one; and the FER structural type, for example,ferrierite. According to the present invention, ZSM-5 is preferably usedas the medium pore zeolite.

According to another embodiment, a blend of large pore and medium porezeolites may be used. The ratio of the large pore zeolite to the mediumpore size zeolite in the cracking catalyst is preferably in the range of99:1 to 70:30, more preferably in the range of 98:2 to 85:15.

The total amount of the large pore size zeolite and/or medium porezeolite that is present in the cracking catalyst is preferably in therange of 5 wt % to 40 wt %, more preferably in the range of 10 wt % to30 wt %, and even more preferably in the range of 10 wt % to 25 wt %relative to the total mass of the cracking catalyst, the remainder beingamorphous binder.

According to the invention, the reaction zone is usually an elongatedtube-like reactor, preferably a vertical reactor in which thelipid-containing feedstock and the cracking catalyst flow in an upwarddirection. The lipid-containing feedstock and the cracking catalyst mayalso flow in a downward direction. Combinations of downward and upwardflow are also within the scope of the present invention. Thelipid-containing feedstock and the cracking catalyst may be contacted incounterflow or crossflow configurations.

According to an embodiment of the invention, the CO₂ produced in thecracking step and the catalyst regeneration step may be reused forcultivation and propagation of the diatomic microalgae being used in theprocess. This process integration preferably mitigates the emissionsfrom the overall process and facilitates cultivation of diatomicmicroalgae.

The product stream can comprise products that may include gaseoushydrocarbons with four or less carbon atoms, gasoline, diesel, cycleoils and other hydrocarbons.

The product stream, comprising cracked hydrocarbons, obtained from theFCC apparatus is preferably sent to a fractionation zone, where it isseparated into one or more hydrocarbon fractions. Preferably, thesehydrocarbon fractions include dry gas, propylene, Liquefied PetroleumGas (LPG), gasoline, light cycle oils and coke. According to anembodiment, the product stream composition includes a gasoline fractionranging from 30 wt % to 60 wt %, preferably from 40 wt % to 50 wt %,based on the total product stream composition, as measured by GasChromatograph Distillation (GCD) according to the methods described inASTM D-2887. Further, the total product stream composition includes aLPG fraction ranging from 5 wt % to 20 wt %, preferably from 10 wt % to15 wt % of the total product stream composition (ASTM D-2887).

These hydrocarbon fractions may undergo further processing before theyare provided for commercial use. Examples of the said processing mayinclude desulfurization, cracking of heavier fractions and addition ofadditives.

The commercial products obtained from these hydrocarbon fractions arealso within the scope of the invention. For example, the gasolinefraction may be desulfurized to reduce the sulfur content to less than1000 ppmw, preferably to less than 500 ppmw, more preferably to lessthan 200 ppmw to prepare a gasoline product. One or more additives maybe added to the desulfurized gasoline product to prepare a gasolinecomposition for commercial use. The additives may include performanceenhancers such as anti-oxidants, corrosion inhibitors, ashlessdetergents, dehazers, dyes, lubricity improvers, synthetic or mineraloil carrier fluids. Examples of such suitable additives may also beidentified in U.S. Pat. No. 5,855,629, which is incorporated herein byreference. For the purpose of the invention, it should be understoodthat the one or more additives can be added separately to the gasolineproduct or can be blended with one or more diluents, forming an additiveconcentrate, and together added to the gasoline product. The gasolinecomposition according to the invention preferably comprises a majoramount (more than 50 wt %) of the gasoline product and a minor amount ofthe one or more additives described above, preferably ranging from 0.005wt % to 10 wt %, more preferably from 0.01 wt % to 5 wt %, and mostpreferably from 0.02 wt % to 1 wt %, based on the gasoline composition.

It may be understood that processing of the aforementioned hydrocarbonfractions is well known in the art and is in no way limiting to thescope of the invention. While some of the methods have been describedherein, several other processes may be used to convert the hydrocarbonfractions into commercially usable products. These processes may includeisomerisation, cracking into more valuable lighter products, blendingwith other fuels for commercial use, and other similar uses that havebeen disclosed in the art.

The invention is further illustrated by the following experiments.

Experiment 1

A batch of marine microalgae of species Chlorella was partially driedand milled. Lipids were then extracted from the marine microalgae usingtoluene as a solvent in a solvent extraction process. The extractedlipids were analysed online using gas chromatography (GC) andinductively coupled plasma mass spectrometry (ICP-MS) and were found tohave the following distribution:

TABLE 1 Extracted lipids from Chlorella microalgae Component Weight %Phospholipids 4.5%  Mono-glyceride  4% Di-glyceride 24% Tri-glyceride58% Free Fatty Acid  9% Total 95%

A blend of 20 wt % of these extracted lipids and 80 wt % of a mineraloil derived vacuum gas oil was mixed. The Blend had the following metalcontent (see table 2 in mg/kg as determined by ICP-AES).

TABLE 2 metal content in a blend of 20 wt % of extracted lipids with 80wt % a mineral oil derived vacuum gas oil (in mg/kg) Al 50 Ca 73 Fe 50Mg 635 Mn 10 Na 92 P 370 Si 52

Experiment 2

The lipids obtained from experiment 1 were blended with mineral VacuumGas Oil (VGO) to form a first batch of the lipid-containing feedstockcomprising 20% extracted lipids from microalgae and 80% VGO (by weight).The first batch was subjected to catalytic cracking in a small-scalefluidised catalytic cracking reactor. A commercial equilibrium catalystcomprising ultra stable zeolite Y (USY) in an amorphous alumina matrixwas used as the cracking catalyst. The reaction temperature was kept at500° C., and the pressure was maintained at 1.1 bar (0.11 MPa). For thefeedstock containing 20 wt % extracted lipids from microalgae and 80 wt% VGO a catalyst to oil ratio of about 8 was used. The product streamobtained was separated in a small-scale fractionator and analysed onlineusing gas chromatography (GC) and inductively coupled plasma massspectrometry (ICP-MS). The results of the experiment with regard toproduct distribution at 67 wt % conversion are provided in Table 3.

TABLE 3 Product distribution Product Yield (wt %) Dry gas 1.9 Propylene2.8 LPG 12.0 Gasoline 43.5 LCO 25.2 HCO 3.2 Slurry Oil 1.75 Coke 9.0

Dry gas includes ethylene and LPG includes propane and butane gas.Gasoline is defined as the fraction starting with C5 isomers, andboiling up to 221° C. (EP); Light Cycle Oil (LCO) as the fractionboiling from 221-370° C. (IBP-EP); Heavy Cycle Oil (HCO) as the fractionboiling from 370-425° C. (IBP-EP); and Slurry Oil as the fractionboiling above >425° C., determined according to ASTM 2887, using thetotal boiling point method.

Experiment 3

To establish the efficacy of the cracking process of the invention, theproduct stream was compared with the products obtained from the crackingof other conventionally used feedstock. VGO was used as the second batchand a blend of 20% rapeseed oil and 80% VGO was used as the third batch.The experiments were conducted in the same fluidised catalytic crackingreactor and under the same conditions as were used in experiment 2,except that a different catalyst to oil ratio may be used to achieve theconstant conversion rate of 67 wt %. A comparison of the product streamobtained from experiments 2 and 3 is provided in Table 4.

TABLE 4 Product yields at constant 67% conversion (wt %) First batch:Second Batch Third 20% lipids Conventional batch: 20% marine algae/cracking feedstock rapeseed 80% VGO batch: VGO only oil/80% VGO Dry gas1.9 1.9 2.0 Propylene 2.8 3.3 3.5 LPG 12.0 13.0 13.0 Gasoline 43.5 46.445.0 LCO 25.2 26.9 24.6 HCO 3.2 3.9 3.5 Slurry Oil 1.75 2.2 2.1 Coke 9.05.8 6.9

The product yield of each batch of cracking feedstock was calculated at67 wt % conversion of the cracking feedstock. It is evident from theresults above that the product stream obtained from the first batch ofcracking feedstock comprising lipids derived from marine microalgae issubstantially similar to the product stream obtained from the twoconventional cracking feedstock. This is highly surprising in view ofthe high content in heteroatoms such as phosphorus and metals. Moreover,the amount of light cycle oil obtained was above that generated fromrapeseed oil.

The additional coke formed in the process according to the invention canbe advantageous when co-processing a further paraffinic feedstock suchas for example an optionally hydroisomerised fraction of the synthesisproduct of a Fisher-Tropsch reaction.

1. A process for catalytic cracking of a lipid-containing feedstock, theprocess comprising contacting the lipid-containing feedstock with atleast one cracking catalyst at a temperature of at least 450° C., toobtain a product stream; and separating at least one hydrocarbonfraction from the product stream; wherein the lipid-containing feedstockcomprises lipids derived from a diatomic microalgae species.
 2. Theprocess of claim 1 wherein the temperature ranges from equal to or morethan 450° C. to equal to or less than 650° C.
 3. The process of claim 1wherein the lipid-containing feedstock further comprises a hydrocarbonfeedstock.
 4. The process of claim 3 wherein the hydrocarbon feedstockcomprises a vacuum gas oil, atmospheric residue or vacuum residue. 5.The process of claim 3 wherein the hydrocarbon feedstock compriseshydrocarbons with an initial boiling point of at least 220° C. asmeasured according to ASTM D-2887.
 6. The process of claim 1 wherein thehydrocarbon feedstock has an initial boiling point of at least 180° C.as measured according to ASTM D-2887.
 7. The process of claim 1 whereinthe lipid-containing feedstock comprises from 2 wt % to 30 wt % lipids.8. The process of claim 7 wherein the lipid-containing feedstockcomprises from 5 wt % to 20 wt % lipids.
 9. The process of claim 2wherein the temperature ranges from equal to or more than 480° C. toequal to or less than 560° C.
 10. The process of claim 1 wherein thecracking catalyst comprises a zeolite.
 11. A gasoline product preparedfrom a hydrocarbon fraction of the at least one hydrocarbon fraction ofclaim
 1. 12. A gasoline product prepared from a hydrocarbon fraction ofthe at least one hydrocarbon fraction of claim
 3. 13. A gasoline productprepared from a hydrocarbon fraction of the at least one hydrocarbonfraction of claim
 4. 14. A gasoline product prepared from a hydrocarbonfraction of the at least one hydrocarbon fraction of claim
 5. 15. Agasoline product prepared from a hydrocarbon fraction of the at leastone hydrocarbon fraction of claim
 6. 16. A gasoline composition havingless than 1000 ppmw sulfur comprising a gasoline product prepared from ahydrocarbon fraction of the at least one hydrocarbon fraction of claim 1and one or more additives.
 17. A gasoline composition having less than1000 ppmw sulfur comprising a gasoline product prepared from ahydrocarbon fraction of the at least one hydrocarbon fraction of claim 3and one or more additives.
 18. A gasoline composition having less than1000 ppmw sulfur comprising a gasoline product prepared from ahydrocarbon fraction of the at least one hydrocarbon fraction of claim 4and one or more additives.
 19. A gasoline composition having less than1000 ppmw sulfur comprising a gasoline product prepared from ahydrocarbon fraction of the at least one hydrocarbon fraction of claim 5and one or more additives.
 20. A gasoline composition having less than1000 ppmw sulfur comprising a gasoline product prepared from ahydrocarbon fraction of the at least one hydrocarbon fraction of claim 6and one or more additives.